KR20180033966A - Novel rhodamine based dyes, colored photosensitive resin composition including the same and color filter manufactured by using this - Google Patents

Abstract

The present invention relates to a rhodamine dye, a colored photosensitive resin containing the same, and a color filter produced by using the colored photosensitive resin. The rhodamine dye of the present invention has excellent solubility in solvents, especially propylene glycol monomethyl ether acetate (PGMEA), and shows excellent heat resistance, color characteristics, molar extinction coefficient, and compatibility with pigments, thereby enabling production of color filters with outstanding luminance, color sharpness, and durability.

Description

[0001] The present invention relates to a rhodamine dye, a colored photosensitive resin composition containing the rhodamine dye, and a color filter manufactured using the same,

The present invention relates to a rhodamine dye, a colored photosensitive resin composition containing the same, and a color filter manufactured using the colored photosensitive resin composition.

Due to the nature of the display industry, the role of the color filter among the various key components of the LCD is the most important in order to obtain a more natural color by implementing clearer colors, sharp contrast and brightness.

Pigments used in color filters are excellent in durability such as heat resistance, light resistance and chemical resistance, but the use of dyes instead of pigments is increasing due to weakness of brightness and contrast ratio due to turbid colors and scattering of light.

In particular, as consumers' desire for display devices such as TVs and smart phones has become increasingly demanding, the pigment particles in the color pastes have tended to become smaller in order to achieve brighter and more distinctive colors. However, And the development is progressing in the direction of partially introducing the dye.

However, dyes are excellent in light color and transparency, but have drawbacks such as poor durability. Therefore, the development of novel dyes having excellent properties and the use of dyes and pigments as a salt pigment hybrid technology are emerging as an alternative.

On the other hand, red color dyes usable in color filters include compounds such as Xanthene, Cyanine, Azo, Anthraquinone, Dioxazine, and Triphenylmethane, among which xanthan and azo compounds having excellent physical properties are mainly used.

The rhodamine dyes in the xanthan family currently used are clear and excellent in color, but have low solubility in organic solvents and low durability such as heat resistance, light resistance, and chemical resistance, and thus have many limitations in use.

Therefore, development of rhodamine dyes having high solubility in propylene glycol monomethyl ether acetate (PGMEA) and improved durability has been required to improve these properties.

Patent Document 1: JP-A-2011-241372 Patent Document 2: Korean Patent Publication No. 10-1361679 Patent Document 3: Korean Patent Publication No. 10-1629066

The present invention relates to a rhodamine dye excellent in solubility in solvents, particularly PGMEA, excellent in thermal stability, color characteristics and compatibility with pigments, and having a high molar extinction coefficient, a colored photosensitive resin composition containing the same, Color filter.

The present invention provides a rhodamine dye excellent in solubility in a solvent, particularly PGMEA, excellent in color characteristics, particularly in brightness and contrast, high in thermal stability, and excellent in affinity with a pigment, Is represented by the following formula (1).

[Chemical Formula 1]

[In the above formula (1)

R ₁ is independently hydrogen, (C ₁ -C ₂₀₎ alkyl, (C ₆ -C ₂₀₎ aryl, (C ₆ -C ₂₀₎ aryl (C ₁ -C ₂₀₎ alkyl, (C ₁ -C _20), respectively alkyl (C ₆ -C ₂₀₎ aryl, (C ₁ -C ₂₀₎ alkoxy (C ₁ -C ₂₀₎ alkyl, hydroxy (C ₁ -C ₂₀₎ alkyl, hydroxy (C ₁ -C ₂₀₎ alkoxy (C (C ₁ -C ₂₀ ) alkyl, (C ₃ -C ₁₀ ) cycloalkyl, halo (C ₁ -C ₂₀ ) alkyl or polyalkoxyalkyl,

A ^- is a halogen-based anion, a sulfonic acid-based anion, an acetic acid-based anion or a phosphorus-based anion.]

Preferably, R ₁ in formula (1) according to an embodiment of the present invention may be polyalkoxyalkyl, and may have a weight average molecular weight of 100 to 1000.

Preferably, the polyalkoxyalkyl according to one embodiment of the present invention may be prepared from ethylene oxide and propylene oxide in a molar ratio of 1: 5 to 10, and may be represented by the following formula 2 or 3:

(2)

(3)

[In the formulas (2) and (3)

R ₁₁ , R ₁₃ and R ₁₄ are each independently (C ₁ -C ₂₀ ) alkylene, R ₁₂ and R ₁₅ are (C ₁ -C ₂₀ )

p, q and r are independently an integer of 1 to 20.]

Preferably, in the formula (1) of the present invention, A ^- represents a bistrifluoromethanesulfonimide anion, a benzenesulfonic acid anion, a 4-methylbenzenesulfonic acid anion, a 4-dodecylbenzenesulfonic acid anion, a naphthalenesulfonic acid anion, a trifluoroacetic acid anion, Methanesulfonic acid anion or hexafluorophosphate anion.

Preferably, the rhodamine dye represented by Formula 1 of the present invention may be represented by Formula 4 or Formula 5 below.

[Chemical Formula 4]

[Chemical Formula 5]

(In the above formulas 4 and 5,

x and y are each independently an integer of 1 to 10,

z is an integer of 10 to 15,

A ^- is a halogen-based anion, a sulfonic acid-based anion, an acetic acid-based anion or a phosphorus-based anion.)

The present invention also provides a colored photosensitive resin composition comprising a rhodamine dye and a pigment of the present invention.

Preferably, the rhodamine dye contained in the colored photosensitive resin composition according to one embodiment of the present invention may be contained in an amount of 0.1 to 20% by weight, and the weight ratio of the rhodamine dye to the pigment may be 1: 0.1 to 10.

Preferably, the colored photosensitive resin composition of the present invention may further comprise one or two or more components selected from a dispersant, a binder resin, a photoinitiator and a crosslinking agent.

The present invention also provides a color filter manufactured using the colored photosensitive resin composition of the present invention.

The rhodamine dyes of the present invention have high solubility in solvents, high molar absorptivity, and excellent thermal stability and chemical resistance.

The rhodamine dyes of the present invention are excellent in affinity with pigments and thus can be easily compatibilized with pigments, so that they are excellent in brightness and color sharpness through hybridization of pigments.

The colored photosensitive resin composition of the present invention has an advantage that the thermostability is excellent by including the rhodamine dye of the present invention and the brightness and color sharpness are not lowered even after the heat treatment.

Therefore, the color filter manufactured using the colored photosensitive resin composition containing the rhodamine dye of the present invention has excellent durability and improved physical properties.

The present invention provides a dye having high durability such as heat resistance, light resistance and chemical resistance and high solubility in a solvent, and the dye of the present invention is represented by the following formula (1).

[Chemical Formula 1]

(In the formula 1,

R ₁ is independently hydrogen, (C ₁ -C ₂₀₎ alkyl, (C ₆ -C ₂₀₎ aryl, (C ₆ -C ₂₀₎ aryl (C ₁ -C ₂₀₎ alkyl, (C ₁ -C _20), respectively alkyl (C ₆ -C ₂₀₎ aryl, (C ₁ -C ₂₀₎ alkoxy (C ₁ -C ₂₀₎ alkyl, hydroxy (C ₁ -C ₂₀₎ alkyl, hydroxy (C ₁ -C ₂₀₎ alkoxy (C (C ₁ -C ₂₀ ) alkyl, (C ₃ -C ₁₀ ) cycloalkyl, halo (C ₁ -C ₂₀ ) alkyl or polyalkoxyalkyl,

A ^- is a halogen-based anion, a sulfonic acid-based anion, an acetic acid-based anion or a phosphorus-based anion.]

The rhodamine dyes of the present invention have excellent durability with a very high solubility in solvents, especially PGMEA.

In addition, the rhodamine dye of the present invention is excellent in affinity with a pigment, maintains the luminance and color sharpness of the dye as it is, and is excellent in thermal stability, so that luminance and color sharpness are not degraded even after the heat process. Has excellent performance.

Preferably, R ₁ in the formula (1) according to an embodiment of the present invention may be polyalkoxyalkyl in view of having excellent brightness, color sharpness and thermal stability.

Preferably, the polyalkoxyalkyl of R < ₁ > according to an embodiment of the present invention may have a weight average molecular weight of 100 to 1000, and preferably a weight average molecular weight of 300 to 750. [

The polyalkoxyalkyl according to one embodiment of the present invention is a polyalkylene oxide group made of (C ₂ -C ₂₀ ) alkylene oxide and having one radical. Examples of the alkylene oxide include propylene oxide, ethylene oxide, And preferably ethylene oxide and propylene oxide may be prepared in a molar ratio of 1: 5 to 10.

Preferably, the polyalkoxyalkyl according to one embodiment of the present invention may be a substituent represented by the following formula (2) or (3).

(2)

(3)

[In the formulas (2) and (3)

R ₁₁ , R ₁₃ and R ₁₄ are each independently (C ₂ -C ₂₀ ) alkylene, R ₁₂ and R ₁₅ are (C ₁ -C ₂₀ )

p, q and r are independently an integer of 1 to 20.]

The rhodamine dye according to an embodiment of the present invention may be a compound having each of the substituents represented by Formula 2 when R ₁ is a substituent represented by Formula 2 or may be a compound having substituents represented by Formula 2 The branch may be a mixture of compounds.

Likewise, the rhodamine dye according to an embodiment of the present invention may be a compound in which R ₁ is a substituent represented by the formula (3), or a compound having each of the substituents represented by the formula (3) alone or a compound having substituents represented by the formula ≪ / RTI >

Preferably, in Formula 2, R ₁₁ is (C ₂ -C ₆ ) alkylene, R ₁₂ is (C ₁₀ -C ₂₀ ) alkyl, and p is an integer of 2 to 5 , R ₁₃ and R ₁₄ are each independently (C ₂ -C ₆ ) alkylene, R ₁₅ is (C ₁ -C ₁₀ ) alkyl, and q and r are each independently an integer of 1 to 20 have.

More preferably, in formula (2), R ₁₁ is (C ₂ -C ₄ ) alkylene, R ₁₂ is (C ₁₀ -C ₁₅ ) alkyl, and p is an integer of 2 to 5 may be, and r ₁₃ and r ₁₄ are each independently alkylene (C ₂ -C ₄₎ in the formula 3, r ₁₅ is (C ₁ -C ₅₎ alkyl, q and r are independently of each other from 1 to 20 May be integers.

Preferably, A < ^- > in the general formula (1) according to an embodiment of the present invention may be a halogen-based anion, a sulfonic acid-based anion, an acetic acid-based anion or a phosphorus-based anion, more preferably a sulfonate-, anacetic- or phosphorus- .

More preferably, A ^- in Formula 1 according to an embodiment of the present invention may be a bistrifluoromethanesulfonimide anion, an trifluoromethanesulfonate anion, an arylsulfonate anion, a trifluoroacetic acid anion, or a hexafluorophosphate anion Specifically, a bistrifluoromethanesulfonimide anion, a benzenesulfonic acid anion, an alkyl-substituted benzenesulfonic acid anion, a 1- or 2-naphthalenesulfonic acid anion, an alkyl-substituted 1- or 2-naphthalenesulfonic acid anion, a trifluoroacetic acid anion, Sulfonic acid anion or hexafluorophosphate anion, and more specifically, an anion such as a bistrifluoromethanesulfonimide anion, a benzenesulfonic acid anion, a 4-methylbenzenesulfonic acid anion, a 4-dodecylbenzenesulfonic acid anion, a naphthalenesulfonic acid anion, a trifluoroacetic acid anion , Trifluoromethane sulphate It may be an acid anion or an anionic phosphate hexafluorotitanate.

In view of excellent durability and solubility, the formula (1) according to an embodiment of the present invention may be represented by the following formula (4) or (5).

[Chemical Formula 4]

[Chemical Formula 5]

(In the above formulas 4 and 5,

x and y are each independently an integer of 1 to 10,

z is an integer of 10 to 15,

A ^- is a halogen-based anion, a sulfonic acid-based anion, an acetic acid-based anion or a phosphorus-based anion.)

Preferably, in the formulas (4) and (5), A ^- is a bistrifluoromethanesulfonimide anion, a benzenesulfonic acid anion, a 4-methylbenzenesulfonic acid anion, a 4-dodecylbenzenesulfonic acid anion, a naphthalenesulfonic acid anion, a trifluoroacetic acid anion, Methanesulfonic acid anion or hexafluorophosphate anion.

The substituents comprising the "alkyl", "alkoxy" and other "alkyl" moieties described in the present invention include both straight chain or branched forms, and "cycloalkyl" includes not only a single ring system but also several cyclic hydrocarbons. &Quot; Aryl " in the present invention means an organic radical derived from an aromatic hydrocarbon by one hydrogen elimination and is a single or fused ring containing 4 to 7, preferably 5 or 6 ring atoms, And includes a form in which a plurality of aryls are connected by a single bond. &Quot; Hydroxyalkyl " means OH-alkyl in which a hydroxy group is bonded to an alkyl group as defined above, and " hydroxyalkoxyalkyl " means hydroxyalkyl- O -alkyl in which an alkoxy group is bonded to the hydroxyalkyl group.

In addition, the '(C ₁ -C ₂₀ ) alkyl' group described in the present invention is preferably (C ₁ -C ₁₀ ) alkyl. The '(C ₆ -C ₂₀ ) aryl' group is preferably (C ₆ -C ₁₈ ) aryl. The (C ₆ -C ₂₀ ) aryl (C ₁ -C ₂₀ ) alkyl 'group is preferably (C ₆ -C ₁₈ ) aryl (C ₁ -C ₁₀ ) alkyl. The (C ₁ -C ₂₀ ) alkoxy (C ₁ -C ₂₀ ) alkyl 'group is preferably (C ₁ -C ₁₀ ) alkoxy (C ₁ -C ₁₀ ) alkyl. The 'hydroxy (C ₁ -C ₂₀ ) alkyl' group is preferably hydroxy (C ₁ -C ₁₀ ) alkyl. The 'hydroxy (C ₁ -C ₂₀ ) alkoxy (C ₁ -C ₂₀ ) alkyl' group is preferably hydroxy (C ₁ -C ₁₀ ) alkoxy (C ₁ -C ₁₀ ) alkyl. '(C ₃ -C ₂₀₎ cycloalkyl "group is preferably (C ₃ -C ₁₀₎ cycloalkyl. The 'polyalkoxyalkyl' group is preferably a poly (C ₂ -C ₂₀ ) alkylene oxide group prepared from ethylene oxide, propylene oxide or mixtures thereof.

Specifically, the R ₁ are each independently hydrogen, methyl, ethyl, n - propyl, i - propyl, n - butyl, i - butyl, t - butyl, n - pentyl, i - pentyl, n - hexyl, i - hexyl , phenyl, naphthyl, biphenyl, terphenyl, anthryl, indenyl, phenanthryl, hydroxymethyl, hydroxyethyl, hydroxy-n - propyl, hydroxy-n - butyl, hydroxy-i - butyl, hydroxy-n -pentyl, hydroxy-i-butyl, hydroxy-n-hexyl, hydroxy-i-hexyl, hydroxymethyl-ethoxyethyl, methoxymethyl, methoxyethyl, methoxypropyl, methoxybutyl, ethoxymethyl, ethoxyethyl Methylphenyl, 4-hexylphenyl, benzyl,? -Methylbenzyl or ethylene oxide, propylene oxide, or mixtures thereof, in the presence of a base such as, for example, methyl, ethyl, propyl, isopropyl, ≪ / RTI >

More specifically, R ₁ is a polyalkoxyalkyl having a molar ratio of ethylene oxide to propylene oxide of 1: 9; Or polyalkoxyalkyl having propylene oxide.

The rhodamine dye according to one embodiment of the present invention may specifically include the following compounds, but the following compounds do not limit the present invention.

(Wherein x or y are each independently an integer of 1 to 10,

 and z is an integer of 10 to 15.)

The rhodamine dyes of the present invention can be prepared as shown in the following Reaction Scheme 1, but it is needless to say that any possible method can be recognized by those skilled in the art.

[Reaction Scheme 1]

[Wherein R ₁ to A ^- are the same as defined in formula (1), and M is hydrogen, sodium or lithium.

The present invention also provides a colored photosensitive resin composition comprising a rhodamine dye and a pigment of the present invention.

The rhodamine dyes of the present invention are excellent in solubility in solvents, particularly PGMEA, and have high affinity with pigments, so that a colored photosensitive resin composition having high durability with excellent brightness and color sharpness by combination of rhodamine dyes and pigments is provided .

That is, the colored photosensitive resin composition of the present invention contains the rhodamine dye of the present invention and a pigment as a colorant and is excellent in color purity and color reproducibility because the luminance is not lowered even after the thermal process, and the durability is remarkably improved .

Hereinafter, the colorant contained in the colored photosensitive resin composition of the present invention will be described in detail.

[coloring agent]

First, the colored photosensitive resin composition of the present invention includes a colorant including the rhodamine dye and the pigment of the present invention to improve durability while maintaining brightness and color sharpness.

The colored photosensitive resin composition of the present invention necessarily contains the rhodamine dye of the present invention as a dye, and the rhodamine dye of the present invention is represented by the above formula (1).

Preferably, R ₁ in formula (1) according to an embodiment of the present invention may be polyalkoxyalkyl, more preferably R ₁ may be polyalkoxyalkyl, and polyalkoxyalkyl has a weight average molecular weight of 100 to 1000 And may be prepared from propylene oxide, ethylene oxide or a mixture thereof, and ethylene oxide and propylene oxide may be prepared in a molar ratio of 1: 5 to 10.

Preferably poly alkoxyalkyl of R ₁ in formula (I) may be represented by the formula 2 or 3.

The rhodamine dye contained in the colored photosensitive resin of the present invention may be contained in an amount of 0.1 to 20% by weight, preferably 1 to 5% by weight.

The dye which is one of the coloring agents contained in the colored photosensitive resin composition according to one embodiment of the present invention can be used by using the rhodamine dye of the present invention alone or by mixing one or more dyes in addition to the rhodamine dye of the present invention.

Specifically, the compound of formula (1) can be used in combination with other acidic dyes, salts of other acidic dyes with metal or nitrogen-containing compounds, derivatives of other acidic dyes, and the like. Specific examples of such dyes include Acid red 29, 31, 51, 52, 92, 94, 97, 133, 134, 158, 176, 183, 198, 249, 266, 289 and 308; Acid Blue 1, 7, 9, 15, 18, 23, 25, 27, 29, 40, 42, 45, 51, 62, 70, 74, 80, 83, 86, 87, 90, 92 , 96, 103, 112, 113, 120, 129, 138, 147, 150, 158, 171, 182, 192, 210, 242, 243, 256, 259, 267, 278, 280, 285, 290, 296, 315 , 324: 1, 335 and 340; Acid Violet 6B, 7, 9, 17 and 19; Direct Violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103 and 104; And Direct Blue 57, 77, 80, 81, 84, 85, 86, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115 , 117, 119, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 166, 167, 170, 171, 172, 173, 188, , 193, 194, 196, 198, 199, 200, 207, 209, 210, 212, 213, 214, 222, 228, 229, 237, 238, 242, 243, 244, 245, 247, 248, , 252, 256, 257, 259, 260, 268, 274, 275, and 293.

The pigment used in the colored photosensitive resin composition according to one embodiment of the present invention can be used without limitation, as long as it is an organic pigment having high transparency, color clarity and heat resistance. Specific examples of the pigment include Pigment Red 177, C.I. Pigment Red 242, C.I. Pigment Red 254, C.I. Pigment Red 255, C.I. Pigment Red 264, C.I. Pigment Red 265, C.I. Pigment Blue No. 15, C.I. Pigment Blue 15: 3, C.I. Pigment Blue 15: 4, C.I. Pigment Blue 15: 6, C.I. Pigment Blue No. 60, C.I. Pigment Blue No. 64, C.I. Pigment Blue 80, C.I. Pigment violet No. 1, C.I. Pigment Violet No. 19, C.I. Pigment Violet 23, C.I. Pigment Violet 29, C.I. Pigment Violet 32, and the like. These organic pigments may be used alone or in combination of two or more.

The color photosensitive resin composition according to an embodiment of the present invention may be used in a weight ratio of rhodamine dye to pigment of 1: 0.1 to 10, preferably 1: 1 to 5.

The colorant according to one embodiment of the present invention may be contained in an amount of preferably 0.1 to 50% by weight, more preferably 0.1 to 20% by weight, based on the total weight of the colored photosensitive resin composition.

The colored photosensitive resin composition according to an embodiment of the present invention may further include one or two or more components selected from dispersants, binder resins, photoinitiators and crosslinking agents in addition to the colorant.

[Dispersant]

 The dispersing agent contained in the colored photosensitive resin composition of the present invention preferably contains an amine group or an ammonium salt group as a pigment-affinity group, and specific examples thereof include an acrylic copolymer, a polyurethane, a polyethylene imine and a mixture thereof . Commercially available dispersing agents include Disperbyk-160, DISPERBIK-161, DISPERBIC-165, DISPERBIC-168, DISPERBIC-170, DISPERBIC-171, DISPERBIC- 2000, Disperby-2001, Disperby-21116, LPN-21116, LPN-22102, LPN-6919, LPN-22251, LPN-22822, LPN-22900, LPN-22238, LPN-21715 and LPN-22474; EFKA-4046, EFKA-4047 and EFKA-4340 from EFKA; Solsperse -5000, Sol Spurs-12000, Sol Spurs-22000, Sol Spurs-24000 and Sol Spurs-32500 from AVECIA; And PB-821, PB-822, PB-824 and PB-827 of Ajinomoto Co., These dispersants may be used alone or in combination of two or more.

The dispersant may be contained in an amount of preferably 1 to 20% by weight, more preferably 1 to 10% by weight based on the total weight of the colored photosensitive resin composition.

[Binder Resin]

The binder resin contained in the colored photosensitive resin composition of the present invention is preferably a linear polymer polymer and soluble in an organic solvent.

Specific examples of the monomers that can be used for the binder resin include compounds having at least one carboxyl group in the molecule (e.g., acrylic acid, methacrylic acid, maleic acid, and fumaric acid); Aromatic vinyl compounds (e.g., styrene,? -Methylstyrene, vinyltoluene, vinylbenzyl methyl ether, benzyl (meth) acrylate, phenyl (meth) acrylate); Unsaturated carboxylate compounds (e.g., methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylate); Compounds having a hydroxyl group (e.g., 2-hydroxyalkyl (meth) acrylate, glycerol (meth) acrylate); (Meth) acrylamide, a secondary or tertiary alkyl acrylamide, a dialkylaminoalkyl (meth) acrylate, N - vinylpyrrolidone, N - vinylcaprolactam, ≪ / RTI >vinyltriazole); Butyl (meth) acrylate, ethylhexyl (meth) acrylate, phenoxyhydroxypropyl (meth) acrylate and the like having a hydrophilic property such as a tetrahydrofurfuryl group, a phosphoric acid moiety, a phosphoric acid ester , A quaternary ammonium salt moiety, an ethyleneoxy chain, a propyleneoxy group, a sulfonic acid group, and the like. These monomers may be used singly or in combination of two or more.

In order to increase the crosslinking efficiency, the resin may have a polymerizable group in the side chain.

The acrylic resin preferably has a weight average molecular weight (measured by GPC method, in terms of polystyrene) of 1,000 to 200,000, more preferably 2,000 to 50,000.

The acrylic resin may be contained in an amount of preferably 1 to 50% by weight, more preferably 1 to 10% by weight based on the total weight of the composition.

[Photo initiator]

As the photoinitiator contained in the colored photosensitive resin composition of the present invention, various photoinitiator compounds commonly known can be used without particular limitation. Specific examples thereof include iodine salt compounds, sulfonium salt compounds, organic halogen compounds, oxime compounds, and mixtures thereof.

The oxime compounds are N -benzoyloxy-1- (4-phenylsulfonylphenyl) butan-1-one-2-imine, N -benzoyloxy- 1- (4-phenylsulfonylphenyl) -imine, N-benzoyloxy-1- (4-phenylsulfonyl-phenyl) -3-cyclopentyl-propan-1-one-2-imine, N-acetyl-1- [9-ethyl-6- (2 Yl) ethane-1-imine, N -acetoxy-1- [9-ethyl-6- {2-methyl- 4- (3,3- -dioxa-bicyclo fentanyl methyloxy) benzoyl} -9 H-carbazole-3-yl] ethane-1-imine, N-acetyl-1- [9-ethyl-6- (2-methylbenzoyl) -9 H - carbazole-3-yl] -3-cyclopentyl-propan-1-imine, N-benzoyloxy-1- [9-ethyl-6- (2-methylbenzoyl) - H-carbazole-3-yl] - 3-cyclopentylpropan-1-one-2-imine and the like. Commercially available products such as Irgacure-369, Irgacure OXE01, OXE02 (manufactured by BASF) and N-1919 (manufactured by ADEKA) may also be used. Among them, N -benzoyloxy-1- (4-phenylsulfonylphenyl) butan-1-one-2-imine, N -benzoyloxy- - imine and N-benzoyloxy-1- (4-phenylsulfonyl-phenyl) -3-cyclopentyl-propan-1-one-2-paper preferably at least selected from the group consisting of imine, and N-benzoyloxy-1- (4-phenylsulfonylphenyl) octan-1-one-2-imine is more preferable. Examples of the alkylphenone compound include 2-methyl-2-morpholino-1- (4-methylsulfonylphenyl) propan- Benzyl butan-1-one and 2- (dimethylamino) -2 - [(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] butan-1-one. Irgacure 369, 907 and 379 (manufactured by BASF) may be used. Examples of the triazine compound include 2,4-bis (trichloromethyl) -6- (4-methoxyphenyl) -1,3,5-triazine, 2,4- (4-methoxynaphthyl) -1,3,5-triazine, 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (Trichloromethyl) -6- [2- (5-methylfuran-2-yl) -1,3,5-triazine, ) Ethenyl] -1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2- (furan-2-yl) ethenyl] Bis (trichloromethyl) -6- [2- (4-diethylamino-2-methylphenyl) ethenyl] -1,3,5-triazine, 2,4- -6- [2- (3,4-dimethoxyphenyl) ethenyl] -1,3,5-triazine.

The photoinitiator may be contained in an amount of preferably 0.1 to 5% by weight based on the total weight of the composition.

[Crosslinking agent]

Specific examples of the crosslinking agent used in the present invention include ethylene glycol di (meth) acrylate, polyethylene glycol di (meth) acrylate having 2 to 14 ethylene groups, trimethylolpropane di (meth) acrylate, trimethylolpropane (Meth) acrylate, pentaerythritol tetra (meth) acrylate, 2-trisacryloyloxymethylethylphthalic acid, propylene glycol di (meth) acrylate, propylene glycol di (Meth) acrylate, dipentaerythritol penta (meth) acrylate, dipentaerythritol hexaacrylate, and dipentaerythritol hexa (meth) acrylate. These crosslinking agents may be used alone or in combination of two or more.

The crosslinking agent may be contained preferably in an amount of 0.5 to 10% by weight based on the total weight of the composition.

[menstruum]

Specific examples of the solvent used in the present invention include propylene glycol monomethyl ether acetate, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, diethylene glycol monomethyl ether, di Alkylene glycol monoalkyl ethers such as ethylene glycol monoethyl ether, and acetic acid esters thereof, ketones such as methyl ethyl ketone, diacetone alcohol, acetone, methyl isobutyl ketone and cyclohexanone, gamma-butyrolactone, Tate, butyl lactate, and ethyl pyruvate.

These solvents may be used alone or in combination of two or more.

The solvent may be used in an amount of preferably 40 to 90% by weight, more preferably 60 to 80% by weight, based on the total weight of the composition.

[Additives (surfactant)]

The composition of the present invention may contain a surfactant as an additive, if necessary, in addition to the above-mentioned components. As the surfactant to be used in the present invention, various commonly known surfactants can be used without particular limitation, and examples of commercially available surfactants include fluorine-based surfactants and silicon-based surfactants having fluorine atoms. These may have a polymerizable group in the side chain. Examples of the fluorine-based surfactant include a surfactant having a fluorocarbon chain in the molecule. Specific examples thereof include Fluorad (registered trademark) FC430, Fluorad FC431 (manufactured by Sumitomo 3M Ltd.), Megapack (registered trademark) F142D, Megapack F171, Megapack F172, Megapack F173, Megapack F177, , Megapack F554, Megapack R30, Megapack RS-718-K (manufactured by DIC Corporation), and the like. Examples of the silicone surfactant having a fluorine atom include a surfactant having a siloxane bond and a fluorocarbon chain in the molecule. Specific examples include Megapac (registered trademark) R08, Megapack BL20, Megapack F475, Megapack F477, and Megapack F443 (manufactured by DIC Corporation). The content of the surfactant is preferably 0.001 wt% to 0.2 wt%, and more preferably 0.002 wt% to 0.1 wt%, based on the total amount of the colored photosensitive resin composition.

The composition according to the present invention can be prepared, for example, by dispersing and dissolving a colorant in a solvent together with a dispersant, an acrylic resin or both, and then adding the remaining components, photoinitiator, crosslinking agent and optional additives.

Hereinafter, for the purpose of a detailed understanding of the present invention, the representative compounds of the present invention will be described in detail by way of synthesis examples, examples, test examples and comparative examples. And the scope of the present invention should not be construed as being limited to the above-described synthesis examples and embodiments. The synthesis examples and embodiments of the present invention are provided to enable those skilled in the art to more fully understand the present invention.

[Synthesis Example 1] Synthesis of 2- [3, 6-bis (diethylamino) -9 H -Xanthen-9-yl] - N  - Preparation of polyetheralkyl-benzamide bistrifluoromethanesulfonimide salt (1)

Reaction 1. 3 ', 6'-bis (diethylamino) -2-polyetheralkyl-spiro [1 H - isoindole-1, 9 '- [9 H ] Xanthene] -3 (2 H )-On( 2 ) synthesis

The rhodamine -B (Rh-B) 2.0 g (3.96 mmol) SURFONAMINE B-60 {CH 3 - [OCH 2 CH 2] x - [OCH 2 CH (CH 3)] y -NH 2, weight-average molecular weight = 600, Huntsman)}, and the reaction solution was slowly heated to react at 200 to 210 ^° C for 8 hours. Then, the reaction mixture was cooled to room temperature, and 40 ml of distilled water was added to the reaction solution. After stirring for 30 minutes, the product was extracted with 40 ml of ethyl acetate. The extracted organic layer was washed with 200 ml of a saturated aqueous solution of sodium hydrogencarbonate and 200 ml of distilled water After washing, the recovered organic layer was dried over anhydrous magnesium sulfate, and the solvent was distilled off under reduced pressure. Purification by silica gel column chromatography (developing solvent; dichloromethane) gave light brown viscous 3 ' , 6 ' -bis (diethylamino) -2-polyetheralkyl-spiro [1 H- '- [9 H]-xanthene] -3 (2 H) - one (2) was obtained 1.42 g (69.3%).

Reaction 2. 2- [3, 6-bis (diethylamino) -9 H -Xanthen-9-yl] - N -Polyetheralkyl-benzamide Bistrifluoromethanesulfonimide salt (< RTI ID = 0.0 > One ) synthesis

3 ', 6' - bis (diethylamino) -2-polyether alkyl-spiro [1 H-isoindole -1,9 '- [9 H] xanthene] -3 (2 H) - one (2) 0.3 g (1.17 mmol) of bistrifluoromethanesulfonimide lithium salt dissolved in 2 ml of dimethylformamide (DMF) was slowly added to the solution at room temperature for 20 minutes, followed by the addition of 1.0 g (0.97 mmol) Stir 2 h. Then, the reaction solution was neutralized with a saturated aqueous solution of sodium hydrogencarbonate and stirred for 30 minutes. The product was extracted with 20 ml of ethyl acetate. The extracted organic layer was washed with 200 ml of distilled water, and the recovered organic layer was dried over anhydrous magnesium sulfate 2, and the solvent was distillated under reduced pressure, a viscous red color of 3, 6-bis (diethylamino) -9 H-xanthene-9-yl] - N-polyether-alkyl-benzamide bis trifluoro methanesulfonamide 1.27 g (99.7%) of imide salt ( 1 ) was obtained.

[Synthesis Examples 2 to 9]

( B-60 ) or SURFONAMINE B-30 ( B-30 ) {NH ₂ [CH (CH ₃ ) CH ₂ O] ₂ - (CH ₂ ) _z CH ₃ , z = 11-13, weight average molecular weight = 325, Huntsman) was used instead of bistrifluoromethanesulfonimide lithium salt, and an anionic salt as shown in Table 1 below was used.

Table 1 below shows the amounts of the amine derivatives, anion salts, synthetic yields, and reaction solvents of Synthesis Examples 2 to 9.

division Amine derivative Anion salt Reaction solvent
/ Usage (ml) Anion salt
usage
(g / mol) yield
(%) Synthesis Example 2 B-60 Benzenesulfonic acid Methanol / 10 0.2 / 0.97 94.0 Synthesis Example 3 B-60 4-methylbenzenesulfonic acid Methanol / 10 0.2 / 0.97 90.3 Synthesis Example 4 B-60 4-dodecylbenzenesulfonic acid Methanol / 10 0.3 / 0.97 97.5 Synthesis Example 5 B-60 2-naphthalenesulfonic acid Methanol / 10 0.3 / 0.97 98.2 Synthesis Example 6 B-60 Trifluoromethanesulfonic acid Methanol / 10 0.2 / 0.97 88.5 Synthesis Example 7 B-60 Trifluoroacetic acid Methanol / 10 0.1 / 0.97 89.5 Synthesis Example 8 B-60 Sodium hexafluorophosphate 50% aqueous acetic acid solution / 40
DMF / 2 0.2 / 1.17 91.4 Synthesis Example 9 B-30 The bistrifluoromethane-
Sulfone imide lithium salt 50% aqueous acetic acid solution / 40
DMF / 2 0.3 / 1.17 67.7

Table 2 shows the solubility, UV-VIS spectrum, TGA and elemental analysis data of each rhodamine dye prepared in Synthesis Examples 1 to 9 in PGMEA.

Rh-B (Sigma-Aldrich) used a commercially available compound.

division PGMEA
Solubility
(%) UV ^*One
TGA ^*2
Elemental analysis % )
λ _max
/ nm ε (x10 ^-4 )
/ M ^-One cm ^-One Calculated value Measures Synthesis Example 1 35 555 3.11 9.9 C: 55.28
H: 7.11
N: 4.30
S: 4.92 C: 52.41
H: 7.24
N: 3.50
S: 4.69 Synthesis Example 2 21 553 0.92 9.3 C: 65.11
H: 8.28
N: 3.56
S: 2.72 C: 62.90
H: 8.11
N: 3.30
S: 3.07 Synthesis Example 3 21 553 0.82 6.1 C: 65.35
H: 8.35
N: 3.52
S: 2.68 C: 64.13
H: 8.31
N: 3.45
S: 2.59 Synthesis Example 4 27 553 0.77 5.1 C: 67.67
H: 9.04
N: 3.12
S: 2.38 C: 65.73
H: 8.92
N: 3.00
S: 2.37 Synthesis Example 5 17 554 0.91 17.5 C: 66.37
H: 8.11
N: 3.41
S: 2.61 C: 62.66
H: 7.71
N: 3.01
S: 3.51 Synthesis Example 6 24 554 4.48 38.7 C: 60.44
H: 7.91
N: 3.58
S: 2.73 C: 56.07
H: 7.56
N: 3.30
S: 3.56 Synthesis Example 7 31 554 2.20 11.6 C: 63.42
H: 8.16
N: 3.70 C: 62.28
H: 8.14
N: 3.62 Synthesis Example 8 31 555 0.75 3.0 C: 59.63
H: 7.94
N: 3.60 C: 65.80
H: 8.90
N: 3.90 Synthesis Example 9 35 555 2.13 5.7 C: 61.47
H: 8.49
N, 4.17
S: 4.77 C: 56.30
H: 8.80
N: 4.40
S: 5.60 Rh-B 0.002> 554 1.79 5.5

* 1: UV measurement solvent; PGMEA

* 2: Weight reduction at 230 ^o C (%)

Table 2 shows that the rhodamine dyes of the present invention are significantly superior to rhodamine-B (Rh-B) in solubility in PGMEA, and that Rh-B has a higher solubility than Rh-B in Synthesis Examples 1, 6, 7 and 9 The rhodamine dyes have a very high molar extinction coefficient and the rhodamine dyes of Synthesis Examples 4 and 8 have very high thermal stability.

[Example 1] Preparation of colored photosensitive resin composition

4.0% by weight of Pigment Red 254, 2.0% by weight of a rhodamine dye of Synthesis Example 1, 2.0% by weight of Dispersive-21116 (BYK-KEMISA) solids as an acrylic dispersant, SPCG-19X (Showa Denko) (Acid value: 110 KOH mg / g, Mw: 10,000) 3.0 wt% based on solids, 30.0 wt% propylene glycol monomethyl ether acetate (PGMEA) and 15.0 wt% diacetone alcohol as a solvent were mixed and agitated, followed by stirring with a bead mill ), 1.0 wt% of SPCG-19X (Showa Denko) (acid value of 110 KOH mg / g, Mw = 10,000) was further added and 1.5 wt% of IRGACURE-369 7.0% by weight of dipentaerythritol hexaacrylate and 0.01% by weight of Megafac F477 (Dainippon Ink and Chemicals) as a surfactant were added in this order. Then, 24.49% by weight of PGMEA and 10.0% by weight of diacetone alcohol were further added, To obtain a red colored photosensitive resin composition.

[Examples 2 to 9] Preparation of colored photosensitive resin composition

A red colored photosensitive resin composition was obtained in the same manner as in Example 1 except that the rhodamine dyes of Synthesis Examples 2 to 9 were used as dyes in Example 1 at 2.0 wt%.

[Comparative Example 1] Preparation of colored photosensitive resin composition

4.0% by weight of Pigment Red 254, 2.0% by weight of Rhodamine-B (Rh-B, Sigma Aldrich Co.), 2.0% by weight of Dispersive-21116 (BYK-KEMISA) solids as an acrylic dispersant, SPCG-19X 3.0% by weight of solid content, 30.0% by weight of propylene glycol monomethyl ether acetate (PGMEA) and 15.0% by weight of diacetone alcohol were mixed and stirred, and the mixture was stirred with a vertical bead mill followed by addition of 1.0 wt% of SPCG-19X (Showa Denko) (acid value 110 KOH mg / g, Mw = 10,000), and 1.5 g of IRGUREURE-369 (BASF) 7.0% by weight of dipentaerythritol hexaacrylate as a crosslinking agent and 0.01% by weight of Megafac F477 (Dainippon Ink and Chemicals) as a surfactant were added in this order. Then, 24.49% by weight of PGMEA and 10.0% by weight of diacetone alcohol were further added Followed by stirring to obtain a red-colored photosensitive resin composition.

[Test Example 1] Color characteristics evaluation test of the colored photosensitive resin composition

Film substrate manufacture:

Each of the colored photosensitive resin compositions obtained in Examples 1 to 9 and Comparative Example 1 was formed into a film using a spin coater and then dried in an oven at 80 ° C for 10 minutes to obtain a coating film. Then, the coated film was exposed to light of 100 mJ / cm ² using an ultra-high pressure mercury lamp and developed for 60 seconds by a spray method using a 0.04% KOH developer (containing 0.12% of a surfactant), and then washed with ultrapure water The developed coating film was thermally cured in an oven at 230 ° C for 20 minutes to prepare a film substrate having a pattern for a color filter.

Color evaluation:

 The xy chromaticity coordinates (x, y) and Y in the XYZ color system of CIE were measured using the characteristic function of the C light source by measuring spectroscopy using the MCPD-3000 colorimeter (manufactured by Ohtsuka) Are shown in Table 3 below.

Contrast evaluation;

The contrast value (maximum luminance value / minimum luminance value, blank value = 20,000) of the film substrate was measured with a contrast system CT-1 (manufactured by Tsubosaka Kikai Co., Ltd.). The results are shown in Table 3 below.

coloring agent x y Y Conversion Y
Ry = 0.327 Y
(%) Contrast value Contrast
(%) Example 1 R254 +
Synthesis Example 1 0.642 0.3273 20.87 16.23 102.71% 4841 115% Example 2 R254 +
Synthesis Example 2 0.642 0.3272 20.61 15.99 101.17% 4454 106% Example 3 R254 +
Synthesis Example 3 0.642 0.3274 20.69 16.03 101.46% 4436 105% Example 4 R254 +
Synthesis Example 4 0.642 0.3274 20.71 16.05 101.59% 4654 110% Example 5 R254 +
Synthesis Example 5 0.642 0.3272 20.68 16.06 101.61% 4801 114% Example 6 R254 +
Synthesis Example 6 0.642 0.3272 20.75 16.13 102.06% 4736 112% Example 7 R254 +
Synthesis Example 7 0.642 0.3275 20.84 16.17 102.30% 4597 109% Example 8 R254 +
Synthesis Example 8 0.642 0.3275 20.78 16.11 101.92% 4684 111% Example 9 R254 +
Synthesis Example 9 0.642 0.3274 20.84 16.18 102.41% 4631 110% Comparative Example 1 R254 + Rh-B 0.642 0.3277 20.51 15.80 100.00% 4218 100%

As shown in Table 3, the film obtained from the colored photosensitive resin composition of the present invention exhibited high brightness and contrast as compared with Comparative Example 1.

Therefore, it was confirmed that the colored photosensitive resin composition of the present invention is very effective for the production of color filters having high brightness and contrast.

The colored photosensitive resin composition of the present invention thus produced exhibits excellent transparency and color clarity while securing thermal stability and light stability while exhibiting little change in transparency and color clarity (contrast) even after thermosetting, thereby producing a color filter excellent in performance and efficiency can do.

Claims (12)

A rhodamine dye represented by the following formula (1).
[Chemical Formula 1]

[In the above formula (1)
R ₁ is independently hydrogen, (C ₁ -C ₂₀₎ alkyl, (C ₆ -C ₂₀₎ aryl, (C ₆ -C ₂₀₎ aryl (C ₁ -C ₂₀₎ alkyl, (C ₁ -C _20), respectively alkyl (C ₆ -C ₂₀₎ aryl, (C ₁ -C ₂₀₎ alkoxy (C ₁ -C ₂₀₎ alkyl, hydroxy (C ₁ -C ₂₀₎ alkyl, hydroxy (C ₁ -C ₂₀₎ alkoxy (C (C ₁ -C ₂₀ ) alkyl, (C ₃ -C ₁₀ ) cycloalkyl, halo (C ₁ -C ₂₀ ) alkyl or polyalkoxyalkyl,
A ^- is a halogen-based anion, a sulfonic acid-based anion, an acetic acid-based anion or a phosphorus-based anion.] In the first aspect,
Wherein R < _{1 >} is a polyalkoxyalkyl. In the second aspect,
Poly alkoxyalkyl is a rhodamine dye having a weight average molecular weight of 100 to 1000 of the R ₁ in the general formula (1). 3. The method of claim 2,
Wherein the polyalkoxyalkyl is prepared from a 1: 5 to 10 molar ratio of ethylene oxide and propylene oxide. In the first aspect,
Of Rhodamine dye to the poly alkoxyalkyl of R ₁ in the formula (1) Substituent represented by the formula (2) or (3).
(2)

(3)

[In the formulas (2) and (3)
R ₁₁ , R ₁₃ and R ₁₄ are each independently (C ₁ -C ₂₀ ) alkylene, R ₁₂ and R ₁₅ are (C ₁ -C ₂₀ )
p, q and r are independently an integer of 1 to 20.] In the first aspect,
In the above formula (1), A ^- represents a bistrifluoromethanesulfonimide anion, a benzenesulfonic acid anion, a 4-methylbenzenesulfonic acid anion, a 4-dodecylbenzenesulfonic acid anion, a naphthalenesulfonic acid anion, a trifluoroacetic acid anion, a trifluoromethanesulfonic acid anion, Rhodamine dye, a hexafluorophosphate anion. In the first aspect,
The rhodamine dye represented by Formula 1 is represented by Formula 4 or Formula 5 below.
[Chemical Formula 4]

[Chemical Formula 5]

(In the above formulas 4 and 5,
x and y are each independently an integer of 1 to 10,
z is an integer of 10 to 15,
A ^- is a halogen-based anion, a sulfonic acid-based anion, an acetic acid-based anion or a phosphorus-based anion.) A colored photosensitive resin composition comprising a rhodamine dye and a pigment according to any one of claims 1 to 7. In the eighth aspect,
Wherein the rhodamine dye is contained in an amount of 0.1 to 20% by weight. In the eighth aspect,
Wherein the rhodamine dye and the pigment are in a weight ratio of 1: 0.1 to 10. In the eighth aspect,
Wherein the colored photosensitive resin composition further comprises one or two or more components selected from a dispersant, a binder resin, a photoinitiator and a crosslinking agent. A color filter produced by using the colored photosensitive resin composition of claim 8.